RU2003103100A - TRIMERIZATION OF OLEPHINS USING A CATALYST, INCLUDING A CHROMIUM SOURCE, MOLYBDENE OR TUNGSTEN AND LIGAND, CONTAINING AT LEAST ONE PHOSPHORUS, MINEROUS GREEN CHEESE - Google Patents

Claims (45)

1. The catalyst, comprising (a) a source of chromium, molybdenum or tungsten, (b) a ligand containing at least one atom of phosphorus, arsenic or antimony, associated with at least one hydrocarbyl or heterohydrocarbyl group, which has a polar Deputy, for except in the case where all such polar substituents are phosphane, arsan or stibane groups, and, optionally, (c) an activator. 2. The catalyst according to claim 1, in which the catalyst is supported on a carrier. 3. A supported catalyst having a productivity per mole of catalyst of at least 50%, preferably at least 70% of its performance, when not supported on a support, more preferably, this catalyst comprises (a) a transition metal source of groups 3 to 10, (b) a ligand containing at least one phosphorus, arsenic, or antimony atom bonded to at least one hydrocarbyl or heterohydrocarbyl group which has a polar substituent, unless all are polar substituents are phosphane, arsan or stibane groups, and optionally (c) an activator. 4. The catalyst according to claim 3, the performance of which relates to the trimerization of olefins. 5. The catalyst according to claim 3 or 4, in which the carrier is selected from silica, alumina, MgCl ₂ , zirconia, polyethylene, polypropylene, polystyrene and polyaminostyrene. 6. The catalyst according to claims 3, 4 or 5, in which component (a) is a source of chromium, molybdenum or tungsten. 7. The catalyst according to any preceding paragraph, in which component (a) is a chromium source. 8. The catalyst according to any preceding paragraph, in which the ligand of component (b) corresponds to the formula (R ¹ ) (R ² ) XYX (R ³ ) (R ⁴ ) or X (R ^l ) (R ² ) (R ³ ) b, in which X denotes an atom of phosphorus, arsenic or antimony; Y is a connecting group; and each of R ¹ , R ² , R ³ and R ⁴ independently from each other represents a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl group, at least one of which in each formula has a polar substituent that is not phosphane, an arsan or stiban group, and any of the groups R ¹ to R ⁴ can be independently associated with one or more of the other groups or with the bridging group Y to form a cyclic structure together with X or with X and Y. 9. The catalyst according to any preceding paragraph, in which X denotes a phosphorus atom. 10. The catalyst of claim 8 or 9, in which the optionally substituted hydrocarbyl or heterohydrocarbyl groups of the radicals R ¹ , R ² , R ³ and R ^{4 are} independently selected from methyl, ethyl, ethylenyl, propyl, butyl, cyclohexyl, benzyl, phenyl, tolyl , xylyl, mesityl, diphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy (i.e., -OC ₆ H ₅ ), tolyloxy [i.e. -OC ₆ H ₄ (CH ₃ )], xyloxy, mesityloxy, dimethylamino, diethylamino, methylethylamino, thiomethyl, thiophenyl, trimethylsilyl and dimethylhydrazyl. 11. The catalyst according to any one of claims 8 to 10, where each of the radicals R ¹ through R ⁴ , which have polar substituents, independently represents a substituted phenyl, substituted naphthyl or substituted anthracenyl group. 12. The catalyst according to claim 11, in which the polar substituents are independently selected from methoxy, ethoxy, isopropoxy, C ₃ -C ₂₀ alkoxy, phenoxy, pentafluorophenoxy, trimethylsiloxy, dimethylamino, methylsulfanyl, tosyl, methoxymethyl, methylthiomethyl, 1,3-oxazolyl, methoxymethoxy, hydroxyl, amino, sulfate, nitro groups, phosphane, arsan and stibane. 13. The catalyst according to item 12, in which each of the radicals from R ¹ to R ⁴ having polar substituents, independently represents o-methoxyphenyl or o-methoxymethoxyphenyl. 14. The catalyst according to any one of claims 8 to 13, in which each of the radicals R ¹ through R ⁴ independently contains a polar substituent that is not a phosphane, arsan or stibane group. 15. The catalyst according to any one of claims 8-14, wherein Y is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted hydrocarbyl or substituted heterohydrocarbyl bridging group or inorganic bridging group. 16. The catalyst of claim 15, wherein Y is methylene, 1,2-ethane, 1,2-phenylene, 1,3-propane, 1,2-catechol, 1,2-dimethylhydrazine, -N (R ⁵ ) -, where R ⁵ denotes a hydrogen atom, hydrocarbyl or substituted hydrocarbyl. 17. The catalyst of claim 16, wherein Y is —N (R ⁵ ) - and R ⁵ is a hydrogen atom, C ₁ -C ₆ alkyl or phenyl. 18. The catalyst according to any preceding paragraph, where component (b) is selected from the following compounds: (2-methoxyphenyl) (phenyl) PN (Me) P (phenyl) _2, (2-methoxyphenyl) ₂ PN (Me) P (phenyl) _2, (2-methoxyphenyl) (phenyl) PN (Me) P (2-methoxyphenyl) (phenyl) _, (2-methoxyphenyl) ₂ PN (Me) P (2-methoxyphenyl) _2, (2-Ethoxyphenyl) ₂ PN (Me) P (2-ethoxyphenyl) _2, (2-Isopropoxyphenyl) ₂ PN (Me) P (2-isopropoxyphenyl) _2, (2-hydroxyphenyl) ₂ PN (Me) P (2-hydroxyphenyl) _2, (2-nitrophenyl) 2PN (Me) P (2-nitrophenyl) _2, (2,3-dimethoxyphenyl) ₂ PN (Me) P (2,3-dimethoxyphenyl) _2, (2,4-dimethoxyphenyl) ₂ PN (Me) P (2,4-dimethoxyphenyl) _2, (2,6-dimethoxyphenyl) ₂ PN (Me) P (2,6-dimethoxyphenyl) _2, (2,4,6-trimethoxyphenyl) ₂ PN (Me) P (2,4,6-trimethoxyphenyl) _2, (2-dimethoxyphenyl) (2-methylphenyl) pH (Me) P (2-methoxyphenyl) _2, [2- (dimethylamino) phenyl] ₂ PN (Me) P [2- (dimethylamino) phenyl] _2, (2-methoxymethoxyphenyl) ₂ PN (Me) P (2-methoxymethoxyphenyl) _2, (2-methoxyphenyl) ₂ PN (ethyl) P (2-methoxyphenyl) _2, (2-methoxyphenyl) ₂ PN phenyl) P (2-methoxyphenyl) _2, (2-methoxyphenyl) ₂ PN (Me) N (Me) P (2-methoxyphenyl) _2, (2-methoxyphenyl) ₂ PCH ₂ P (2-methoxyphenyl) _2, (2-methoxyphenyl) ₂ PCH ₂ CH ₂ P (2-methoxyphenyl) _2, tri (2-methoxymethoxyphenyl) phosphane, i.e.

tri (2-methoxyphenyl) phosphane. 19. The catalyst according to any one of the preceding claims, wherein component (c) is selected from trimethylaluminium (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminium dichloride, ethylaluminium chloride, aluminum, aluminum chloride, dimethylaluminium chloride, aluminum, aluminum tetrafluoroboric acid ester, silver tetrafluoroborate, sodium hexafluoroantimonate, boroxins, NaBH ₄ , trimethylboron, triethylboron, dimethylphenylammonium tetra (phenyl) borate, trityl tetra (phenyl) borate, three phenylboron, dimethylphenylammonium tetra (pentafluorophenyl) borate, tetrakis [(bis-3,5-trifluoromethyl) phenyl] sodium borate, H ⁺ (OEt ₂ ) ₂ [(bis-3,5-trifluoromethyl) phenyl] borate, trityl tetra (pentafluorophenyl) borate , tris (pentafluorophenyl) boron and mixtures thereof. 20. A catalyst for the trimerization and polymerization of 1-olefins, further comprising one or more catalysts (g) suitable for polymerization, oligomerization or other chemical transformations of olefins. 21. The catalyst according to claim 20, in which the catalyst (d) is selected from ziegler-natta catalysts, metallocene catalysts, monocyclo-pentadienyl catalysts or "geometry-constrained" catalysts activated by heating chromium oxide catalysts on supports, newly created transition metal catalysts and polymerization catalysts with a single plot. 22. The catalyst according to any preceding paragraph, the trimerization capacity of which is at least 15,000 g of product per millimole of catalyst per hour, preferably at least 30,000 g of product per millimole of catalyst per hour, at a temperature of 110 ° C. or less and a partial pressure of ethylene 21 bar or less. 23. An olefin trimerization catalyst in which productivity decreases at a rate of less than 10% / h. 24. An ethylene trimerization catalyst in which the trimerization capacity is at least 15,000 g of product per millimol of catalyst per hour, preferably at least 30,000 g of product per millimol of catalyst per hour, at a temperature of 110 ° C. or less and a partial pressure of ethylene of 21 bar or less. 25. The catalyst according to any one of paragraphs.22-24, which is applied to a carrier, preferably to a carrier selected from silica, alumina, MgCl ₂ , zirconia, polyethylene, polypropylene, polystyrene and polyaminostyrene. 26. A method for the trimerization of olefins, comprising introducing a monomeric olefin or a mixture of olefins under trimerization conditions into contact with a catalyst that includes (a) a transition metal source of groups 3 to 10, (b) a ligand containing at least one phosphorus, arsenic atom, or antimony associated with at least one hydrocarbyl or heterohydrocarbyl group which has a polar substituent, unless all such polar substituents are phosphane, arsenic or stibane groups, and optionally no, (c) an activator. 27. The method according to p, in which the catalyst is a catalyst according to any one of claims 1 to 25. 28. The method according to p. 26 or 27, in which the olefin or mixture of olefins is additionally brought into contact with another catalyst suitable for polymerization, oligomerization or other chemical transformations of olefins, as a result of which the trimerization products are introduced into the polymer of a higher molecular weight or other chemical product. 29. The method according to any one of claims 26 to 28, wherein the monomeric olefin is ethylene. 30. The method according to any one of claims 26 to 28, wherein the olefin mixture comprises ethylene and one or more C ₃ -C ₃₆ monoolefins. 31. The method according to claim 30, wherein the C ₃ -C ₃₆ monoolefin is a C ₄ -C ₂₀ monoolefin. 32. The method according to p, in which the C ₄ -C ₂₀ monoolefin includes butene, hexene, decene, C ₁₂ olefin or C ₁₄ olefin. 33. The method according to any one of p-32, in which at least 85 wt.%, Preferably at least 90 wt.%, Of the product of the trimerization reaction is one of the following compounds: 1-hexene, 1-octene, 1-decene, C ₁₂ olefin, C ₁₄ olefin, C ₁₆ olefin or C ₁₈ olefin. 34. The method according to any one of claims 26-33, wherein the reaction temperature is less than 100 ° C and / or the absolute reaction pressure is less than 30 bar. 35. The method according to any one of claims 26-34, wherein the residence time in the polymerization reactor is less than 4 hours, preferably less than 3 hours. 36. The method according to any one of claims 26-35, wherein the reaction conditions are the conditions of the solution phase, suspension phase or gas phase. 37. The method according to clause 36, in which the reaction is carried out under conditions of a gas phase in a fluidized bed. 38. The method according to p, in which the trimerization reactor is placed in the production line before or after at least one polymerization or oligomerization reactor. 39. The method according to p, in which the trimerization reactor is included in the reaction loop of at least one polymerization or oligomerization reactor. 40. The method according to § 39, in which the trimerization reactor is included in the side stream discharged from the reaction loop. 41. The method according to p, in which the product of the trimerization reaction is obtained or introduced into at least one polymerization or oligomerization reactor. 42. The method according to any one of claims 28 and 38-40, wherein at least one product of the trimerization reaction is separated from the remaining products of the trimerization reaction before (re) entering the polymerization or oligomerization reactor. 43. The method according to any one of claims 26-42, wherein the trimerization reaction is carried out in the presence of hydrogen and / or a halide source. 44. The use of a mixture of components (a), (b), optionally (c) and, optionally, (d), as presented in claims 1 to 25, as a catalyst for the trimerization of olefins. 45. The use of a mixture of components (a), (b), (d) and, optionally, (c), as presented in claims 1 to 25, as a catalyst for the homopolymerization of ethylene to produce polyethylene having a density of 960 g / cm or less, preferably 940 g / cm or less, and more preferably 920 g / cm or less.